Systems, apparatus, and methods for stabilizing hydrofluoroolefins in refrigerant systems

Abstract

The present invention relates to systems, apparatuses, and methods for preparing and charging into a refrigerant circuit any of: (1) a fluoroolefin refrigerant composition stabilized with an inhibitor that prevents or reduces oligomerization or polymerization of the fluoroolefin component of the composition, and (2) a refrigerant composition stabilized with an inhibitor that prevents or reduces polymerization of the fluoroolefin component of the composition; or (2) a fluoroolefin refrigerant composition purified by removal of the inhibitor; and / or maintaining the integrity of the fluoroolefin refrigerant composition in a refrigeration plant by circulating the fluoroolefin refrigerant composition in the refrigerant plant through one or more columns or devices to remove oxygen and at least one of oxygen-containing contaminants, moisture / moisture, oligomeric / polymeric by-products.

Description

Background Art Technical Field

[0001] The present invention relates to multifunctional systems and methods that are capable of stabilizing and / or purifying fluoroolefin refrigerant or heat transfer compositions for use in refrigeration or heat transfer equipment and maintaining the stability / integrity of fluoroolefin refrigerant compositions or fluoroolefin heat transfer compositions for use in refrigeration or heat transfer equipment, wherein the fluoroolefins are susceptible to oligomerization or polymerization in the presence of air, oxygen and / or oxidizing compounds or contaminants.

[0002] Related technologies

[0003] Heat transfer fluids or refrigerants consisting of 2,3,3,3-tetrafluoropropene (HFO-1234yf) refer to molecules that are stable under heat transfer or refrigeration use conditions. However, HFO-1234yf may oligomerize or homopolymerize in the presence of air and oxidizing chemicals during storage and / or use. It has also been observed that certain fluoroolefins may exhibit degradation and / or produce by-products that should be removed under abnormal conditions that may occur unexpectedly in specific uses and / or applications, such as extreme temperatures or when in contact with other compounds in contaminated systems (e.g., excess oxygen, oxidizing chemicals or free radical generating compounds, and various pollutants). This degradation may occur by any number of different mechanisms.

[0004] One solution is to provide stabilizing compositions as disclosed in JP 2009298918, US 6,969,701, US 8,133,407, US 2006 / 0022166, US 2006 / 0043330, US 2008 / 0157022 and WO 2007 / 126760, as well as EP 2057245, US 8101094, US 8535555, US 8097181 and US 8075796, the disclosures of each of which are hereby incorporated by reference in their entirety.

[0005] Another solution has been proposed in which a fluoroolefin-containing composition (e.g., 2,3,3,3-tetrafluoropropylene) is modified to include an effective amount of an oligomerization / polymerization inhibitor, including at least one of limonene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol, as disclosed in each of U.S. Patent Publication Nos. US20210108119 and US202100430368, the disclosures of each of which are hereby incorporated by reference in their entirety. However, while these inhibitor compounds react effectively with oxygen and / or act as chain transfer agents to terminate polymer chain growth due to the fluoroolefin, their presence can also reduce the purity of the refrigerant entering the heat transfer system (e.g., refrigerant system).

[0006] Therefore, there is a need for an alternative method for inhibiting the oligomerization / polymerization of the fluoroolefin component of refrigerant / heat transfer compositions in heat transfer / refrigeration systems and equipment so as to maintain the integrity of the system and the fluoroolefin-containing composition regardless of the addition or presence of an oligomer / polymer inhibitor. Summary of the invention

[0007] The present invention relates to systems, apparatus and methods which inhibit the oligomerization / polymerization of the fluoroolefin component of a refrigerant / heat transfer composition in a heat transfer / refrigeration system and apparatus so as to maintain the integrity of the system and the fluoroolefin-containing composition, regardless of the presence of an oligomer / polymer inhibitor.

[0008] The present invention relates to systems, apparatus, kits, and methods for (1) charging a refrigerant circuit with a fluoroolefin refrigerant composition stabilized with an inhibitor that prevents or reduces oligomerization or polymerization of the fluoroolefin component of the composition; or (2) charging a system with a fluoroolefin refrigerant composition that does not contain an oligomerization or polymerization inhibitor, the system being designed to maintain the integrity of the fluoroolefin refrigerant composition and the system by circulating the fluoroolefin refrigerant composition through one or more treatment zones, and optionally configured to receive a pressurized source of an inhibitor-containing fluoroolefin composition feed containing an effective amount of an inhibitor, the treatment zones eliminating / removing oxygen or oxidative contaminants, eliminating / removing moisture, and eliminating or removing oligomer / polymer products and by-products.

[0009] The present invention provides multifunctional systems, modifications and methods that eliminate or reduce undesirable oligomerization / polymerization of the fluoroolefin component of a heat transfer / refrigerant composition by optionally adding an effective amount of an oligomerization / polymerization inhibitor of up to 1 weight percent (wt % or mass %), more specifically 0.02 wt % to 0.5 wt %, to a refrigerant circuit comprising various treatment stages through which the fluoroolefin refrigerant composition passes to remove oxygen and oxygen-containing contaminants, remove moisture and / or remove any in-situ generated oligomeric or polymeric byproducts, wherein the fluoroolefin composition comprises HFO-1234yf, optionally R-32, R-125, R-152a, RE-HFO-1234ze, R-134a, R-227ea, RE / Z-1336mzz, CO 2 , RE / Z-1132, at least one of R-1132a.

[0010] The present invention discloses a fluoroolefin-containing composition comprising HFO-1234yf, optionally containing R-32, R-125, RE-HFO-1234ze, R-134a, R-227ea, RE-1336mzz, CO 2 , RE / Z-1132, R-1132a, R-152a, and passed through a cartridge filled with at least one oligomerization / polymerization inhibitor such as limonene, terpinene, pinene at a rate sufficient to add an effective amount of the inhibitor sufficient to prevent the oligomerization / polymerization of at least HFO-1234yf, and can then be loaded into the refrigerant / heat transfer system / equipment.

[0011] Disclosed herein are kits comprising a cartridge and a pressurized cartridge of a fluoroolefin-containing composition filled with at least one oligomerization / polymerization inhibitor such as limonene, terpinene, pinene (e.g., an oxidation product inhibitor) to add an effective amount of the inhibitor to at least prevent HFO-1234yf oligomerization / polymerization, the fluoroolefin-containing composition comprising HFO-1234yf, optionally containing R-32, R-125, R-152a, RE / Z-HFO-1234ze, R-134a, R-227ea, RE / Z-1336mzz, CO 2 , RE / Z-1132 and R-1132a.

[0012] Disclosed herein are kits comprising a pressurized cylinder of a fluoroolefin-containing composition comprising a lubricant and at least one oligomerization / polymerization inhibitor selected from the group consisting of: (1) d-limonene, levo-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene and mixtures of two or more thereof, and (2) ethane, propane, cyclopropane, propylene, butane, butylene, isobutane, isobutylene, 2-methylbutane, m-xylene, o-xylene or p-xylene, α, methylstyrene; α,2-dimethylstyrene; α,3-dimethylstyrene; or α,4-dimethylstyrene, to at least prevent HFO-1234yf oligomerization / polymerization.

[0013] Disclosed herein are HFO-1234yf fluoroolefin-containing compositions containing one or more of limonene, terpinene, pinene (i.e., oxidation product inhibitors) wherein a tower is used to remove the inhibitors and produce a pure stream of the HFO-1234yf fluoroolefin-containing composition which is then fed to a heat transfer / refrigeration device.

[0014] Disclosed herein are multifunctional systems, modifications and methods for maintaining the integrity of refrigerants circulating through refrigeration equipment, whether or not they contain stabilized or purified HFO-1234yf-containing fluoroolefin compositions, by reducing, avoiding, eliminating and removing oligomeric / homopolymerizing materials and oligomeric / polymer by-products from circulating HFO-1234yf-containing fluoroolefin compositions through the use of one or more oxygen / air / oxygen-containing / oxidative contaminant removal towers, water removal / dehumidification dryers, one or more systems for removing and / or reducing oligomeric / polymeric by-products.

[0015] Disclosed herein are systems, components and methods for preventing and / or reducing undesirable oligomeric / polymeric fluoroolefin byproducts of fluoroolefin-containing refrigerants by adding an effective amount of an oligomer / polymer inhibitor to the fluoroolefin-containing refrigerant and then charging the fluoroolefin-containing refrigerant into a refrigerant apparatus, the oligomer / polymer inhibitor comprising at least one of terpenes, terpenoids, terpinenes, linear unsaturated hydrocarbons and mixtures of two or more thereof. The apparatus is new, existing or retrofitted to include one or more oxygen / air / oxygen-containing / oxidative contaminant removal towers, water removal / dehumidification dryers, one or more systems for removing and / or reducing oligomeric / polymeric byproducts in a fluoroolefin composition fluid containing HFO-1234yf circulating in the apparatus or system.

[0016] Disclosed herein are methods and systems comprising one or more oxygen / air / oxygen-containing / oxidizing contaminant removal towers using supported or unsupported deoxygenators that react with or remove oxygen / air / oxygen-containing / oxidizing compounds that promote the oligomerization / polymerization of the fluoroolefin component of a refrigerant composition circulating in a refrigeration device without cleaving the C-F bonds of the fluoroolefins.

[0017] Disclosed herein are systems and methods using an apparatus or tower filled with a deoxygenation agent suitable for removing oxygen from a mixture containing fluoroolefins, optionally at room temperature (e.g., 20° C. to 30° C.), and including, but not limited to, zero-valent or low-valent transition metals and reduced oxides of transition metals, wherein the transition is selected from Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd. Zero-valent or low-valent transition metals and reduced oxides of transition metals are commercially available or can be prepared by heating transition metal oxides in a reservoir such as a tube or tower at elevated temperatures (100° C. to 300° C.) in the presence of a reducing agent such as hydrogen. Examples of metal oxides suitable for reduction in this manner include, but are not limited to, CuO, TiO 2 、V 2 O 5 , Mn 2 O 3 , Fe 2 O 3 、Co 3 O 4 , ZnO, NiO and PdO. Other deoxygenation agents include ascorbate, NaHSO 4 、Na 2 SO 3 、Na 2 S 2 O 5 、Na 2 S 2 O 3 、Na 2 S 2 O 2 , solutions of polyhydroxybenzene compounds such as pyrogallol; Ti(III) salts, Cr(II) salts, Sn(II) salts, Fe(II) salts; nitrites and hypophosphites.

[0018] Oxygen may be removed from the fluoroolefin composition by passing the fluoroolefin mixture through a tower or bed of a deoxygenating agent at 20°C to 30°C without cleaving the CF bonds of at least the HFO-1234yf fluoroolefin component of the composition.

[0019] Disclosed herein are multifunctional systems, modifications and methods that can: (1) eliminate or reduce undesirable oligomerization / polymerization of a fluoroolefin component of a refrigerant by adding an effective amount of an oligomer / polymer inhibitor to a heat transfer / refrigerant composition or blend or a source of the refrigerant composition or blend (e.g., a storage reservoir such as a container, tank or drum) prior to loading into a heat transfer / refrigerant system or heat transfer / refrigeration loop; or (2) remove the inhibitor from a stabilized heat transfer / refrigerant contained in a storage tank, container or drum to provide a pure, substantially inhibitor-free heat transfer / refrigerant composition to be added to a new, existing or retrofitted heat transfer / refrigerant system or loop that includes means for eliminating, removing or reducing oxygen / air, moisture, oligomer / polymer byproducts from the circulating fluid of the heat transfer / refrigeration loop through the use of one or more filters and / or separators and optionally provided with a fresh source of stabilized refrigerant or refrigerant composition blend.

[0020] Also disclosed herein are systems and methods for preventing and / or reducing the formation of oligomeric and homopolymeric products and byproducts adapted to add an effective amount of at least one oligomerization / polymerization inhibitor to a fluoroolefin-containing heat transfer / refrigerant composition or a source of circulating fluoroolefin heat transfer / refrigerant compositions, wherein the inhibitor is selected from one of dextrorotatory limonene, levorotatory limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene and mixtures of two or more thereof.

[0021] Also disclosed herein are systems and dispensing techniques by which at least one of d-limonene, levo-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene, and mixtures of two or more thereof, is dispensed / metered into a flowing stream of a composition containing 2,3,3,4-tetrafluoropropene to stabilize the composition from oligomerization and / or polymerization.

[0022] Also disclosed herein are methods and apparatus for providing a flowable supply of a fluoroolefin heat transfer / refrigerant composition stabilized with an effective amount of at least one of d-limonene, levo-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, i.e., an inhibitor for loading into a refrigerant system.

[0023] Also disclosed herein is a system comprising a kit comprising a prepackaged / self-contained composition supply source and a cartridge containing an inhibitor, the composition comprising at least HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, HFO-1132a and CO2, the cartridge comprising a carrier-supported or unsupported oligomer inhibitor such as d-limonene, levo-limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene and a mixture of two or more, or the inhibitor can be added to the lubricant or formulated with the lubricant for use during oil change. The lubricant is conducive to the addition of a higher concentration of the inhibitor.

[0024] In one embodiment of the invention, the kit includes a prepackaged / stand-alone lubricant and an inhibitor supply, the inhibitor including: d-limonene, levo-limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene and mixtures of two or more, or ethane, propane, cyclopropane, propylene, butane, butylene, isobutane, isobutylene, 2-methylbutane, m-xylene, o-xylene or p-xylene, one of the following: α, methylstyrene; α,2-dimethylstyrene; α,3-dimethylstyrene; or α,4-dimethylstyrene.

[0025] In another embodiment of the present invention, the kit includes a prepackaged / self-contained lubricant supply and a cartridge filled with an inhibitor, the inhibitor including: d-limonene, levo-limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene and mixtures of two or more, or ethane, propane, cyclopropane, propylene butane, butylene, isobutane, isobutylene, m-xylene, o-xylene or p-xylene, one of the following substances: α-methylenestyrene, α, methylstyrene; α,2-dimethylstyrene; α,3-dimethylstyrene; or α,4-dimethylstyrene, the inhibitor can be added to the lubricant during a refrigerant circuit oil change.

[0026] Also disclosed herein is a system comprising a kit comprising a prepackaged / self-contained HFO-1234yf-containing composition, a lubricant, and a supply of an inhibitor, the inhibitor comprising dextrorotatory limonene, levorotatory limonene, alpha-pinene, beta-pinene, alpha-terpinene, beta-terpinene, gamma-terpinene, and delta-terpinene, and mixtures of two or more thereof, or comprising a supply of a lubricant and a cartridge adapted to add an inhibitor during an oil change, the inhibitor comprising: dextrorotatory limonene; Limonene, levorotatory limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene and mixtures of two or more thereof, or ethane, propane, cyclopropane, propylene, butane, butylene, isobutane, isobutylene, 2-methylbutane, m-xylene, o-xylene or p-xylene, one of the following: α, methylstyrene; α, 2-dimethylstyrene; α, 3-dimethylstyrene; or α, 4-dimethylstyrene.

[0027] Also disclosed herein is a system apparatus comprising a refrigeration circuit for conveying a fluoroolefin refrigerant composition and comprising at least one compressor, at least one evaporator, at least one condenser, at least one expansion device (which is an orifice, a capillary tube or an expansion valve), at least one dryer for dehumidification and optionally at least one of the following: at least one service valve; a stabilized refrigerant charging subsystem or kit; a purified refrigerant charging subsystem; a subsystem for separating oligomers / polymers; and an oligomer / polymer filter.

[0028] Also disclosed herein is a system comprising a refrigeration circuit for circulating a fluoroolefin refrigerant composition and comprising a compressor, an evaporator, a condenser, a dryer for dehumidification or water removal (which comprises a filter section and a dryer section) and a stabilized refrigerant charging subsystem.

[0029] Also disclosed herein is a system comprising a refrigeration circuit for conveying a fluoroolefin refrigerant composition and comprising a compressor, an evaporator, a condenser, a dryer for dehumidification or water removal, and a purified refrigerant charging subsystem and an optional stabilized refrigerant charging subsystem.

[0030] Also disclosed herein is a system comprising a refrigeration circuit for conveying a fluoroolefin refrigerant composition and comprising a compressor, an evaporator, a condenser, at least one dryer for removing moisture or water, at least one (1) system for removing oxygen and / or oxidizing compounds (including a deoxidizer) and / or (2) system for separating oligomers / polymers (including an oligomer / polymer filter), wherein an air or oxygen detector or sensor is associated with the vapor space of the refrigerant in the container or a portion of the refrigeration circuit to control the use of the deoxidizer.

[0031] Also disclosed herein are any of the disclosed devices, systems, and uses thereof, and combinations of transport components or service facilities for automobiles, trucks, railcars, or other transport systems, any mobile carriers (referred to as "combined" systems, such as combined systems including "containers" (combined sea / land transport) and "detachable boxes" (combined road and rail transport)). BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 A first embodiment is shown depicting a system for providing an inhibitor-containing fluoroolefin composition to a refrigeration circuit.

[0033] Figure 2 A system for removing inhibitors from a fluoroolefin composition and charging the purified fluoroolefin composition into a refrigeration circuit is shown.

[0034] Figure 3 A refrigeration circuit is shown, which includes a refrigeration circuit for removing O 2 Free-standing towers for oxidative contaminants, moisture removal, and oligomer / polymer by-product removal.

[0035] Figure 4 A refrigerant circuit is shown including an integrated oil separator / polymer filter for returning oil in the compressor discharge line to the compressor.

[0036] Figure 5 An integrated oil / polymer filter is shown for flowing compressor oil from the compressor sump to the compressor lubrication surfaces via a shaft driven oil pump or and external oil pump.

[0037] Figure 6 shows the Opteon TM systems that operate on-product and stabilizer injection kits for dosing additional stabilizer into a system already filled with a refrigerant composition. DETAILED DESCRIPTION

[0038] The foregoing summary and the following detailed description are exemplary and explanatory only and do not limit the invention as defined in the appended claims. Other features and benefits of any one or more embodiments will be apparent from the following detailed description and claims.

[0039] Refrigerants such as fluoroolefin HFO-1234yf are stable molecules under normal refrigeration use conditions. However, 2,3,3,3-tetrafluoropropene (HFO-1234yf, R-1234yf or 1234yf) may oligomerize or homopolymerize in the presence of air / oxygen, oxidizing chemicals or free radical generating compounds during storage. It has also been observed that certain fluoroolefins (e.g., HFO-1234yf) may exhibit degradation and / or produce oligomeric / polymer byproducts under abnormal conditions that may occur unexpectedly in specific uses and / or applications and should preferably be removed using a subsystem containing a deoxidizer that can respond to the detection of air / oxygen by a sensor (such as extreme temperatures or contact with other compounds in a contaminated system (e.g., excess oxygen, oxidizing chemicals or free radical generating compounds, and various contaminants). Such degradation may occur during storage or transportation, or when fluoroolefins are utilized as refrigerants or heat transfer fluids. One solution to avoid oligomerization / homopolymerization / polymerization to form by-products is to use various inhibitors such as terpenes, terpenoids, terpinenes, linear unsaturated hydrocarbons, such as those disclosed in commonly owned U.S. Patent Publication Nos. 20210108119 and 2021004036, the disclosures of each of which are hereby incorporated by reference in their entirety, which stabilize the hydrofluoroolefin component (e.g., HFO-1234yf) from oligomerization / homopolymerization / polymerization.

[0040] Before addressing the details of the embodiments described herein, some terms are defined or clarified as follows.

[0041] As used herein, a refrigerant is a compound or mixture or blend of compounds, such as a refrigerant composition, used as a heat transfer fluid in a cycle wherein the fluid optionally undergoes a phase change from liquid to gas and back to liquid.

[0042] As used herein, the term fluoroolefins has been described compounds that comprise carbon atoms, fluorine atoms and optional chlorine and / or hydrogen atoms. In one embodiment, the fluoroolefins used for the compositions of the present invention include compounds with 2 to 12 carbon atoms. In another embodiment, the fluoroolefins include compounds with 3 to 10 carbon atoms, and in yet another embodiment, the fluoroolefins include compounds with 3 carbon atoms. Representative fluoroolefins and chlorofluoroolefins include, but are not limited to, the compounds listed in the following table 1.

[0043] Table 1

[0044]

[0045] As used herein, the terms "comprises," "including," "having," or any other variation thereof, are intended to encompass non-exclusive inclusions. For example, a process, method, article, or device that includes a list of elements need not be limited to only those elements, but may include other elements that are not expressly listed or that are inherent to such process, method, article, or device. In addition, unless expressly indicated to the contrary, "or" refers to an inclusive or and not an exclusive or. For example, a condition A or B satisfies any of the following conditions: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0046] The transitional phrase "consisting of" excludes any unspecified elements, steps, or ingredients. If in a claim, protection is not included for materials other than those recited, except for impurities normally associated therewith. When the phrase "consisting of" appears in a clause in the body of a claim, rather than immediately following the preamble, it limits only the elements recited in that clause; other elements are not excluded from the claim as a whole.

[0047] The transitional phrase "consisting essentially of" is used to define a composition, method, or process that includes materials, steps, features, components, or elements in addition to those disclosed in the document, provided that these additionally included materials, steps, features, components, or elements do not significantly affect the basic and novel features of the claimed invention, especially the mode of action for achieving any desired result in the method of the invention. The term "consisting essentially of" occupies an intermediate position between "comprising" and "consisting of."

[0048] Where the applicant has defined an invention or a portion thereof using open-ended terms such as “comprising,” it should be readily understood that (unless otherwise indicated) the description should be interpreted as also including such inventions using the terms “consisting essentially of” or “consisting of.”

[0049] In addition, the use of "a" or "an" is used to describe elements and components described herein. This is for convenience only and to give a general sense of the scope of the invention. The description should be understood to include one or at least one, and the singular also includes the plural, unless it is obvious that there is another meaning.

[0050] In addition, disclosed herein are methods and systems comprising one or more steps or components that may or may not be integrated with each other. In certain embodiments, components and methods of use are integrated with each other, while in other embodiments, some of these steps or components may be associated with other systems and processes.

[0051] In certain disclosed embodiments, any of the disclosed devices, systems, and uses thereof, is part of or in combination with a component or service facility for an automobile, truck, railcar, or other transportation system, or any mobile carrier (referred to as a "combined" system, such as a combined system including "containers" (combined sea / land transport) and "disconnectable boxes" (combined road / rail transport)).

[0052] The fluoroolefins or blend compositions disclosed herein include, but are not limited to, compositions comprising HFO-1234yf alone or compositions comprising HFO-1234yf and 1,1,1,3-tetrafluoropropylene (HFO-1234ze, R-1234ze or 1234ze) and optionally comprising an additional compound selected from the group consisting of:

[0053] a)HFO-Z / E-1225ye;

[0054] b) HFO-Z / E-1225ye and HFC-32;

[0055] c) HFO-Z / E-1225ye and HFC-134a;

[0056] d) HFO-Z / E-1225ye, HFC-134a and HFC-32;

[0057] e) HFO-Z / E-1225ye and HFO-1234yf; or

[0058] f) HFO-Z / E-1225ye and HFC-125.

[0059] Additional fluoroolefin compositions comprise at least one of HFO-1234yf and HFO-1234ze and a blend of: i) R-134a, R-32, and R-125; ii) R-134a; iii) R-227ea; iv) R-236fa; and v) R-134, including but not limited to commercially available blends, including but not limited to Opteon TM XL10, XP10, XP20, XP40, XP44, and commercially available HFO-1234ze blends such as R-448A from Honeywell International and sold by Daikin Global.

[0060] In certain embodiments of the present invention, the refrigerant components and fluoroolefin compositions also include those identified in commonly owned U.S. Patent Publication Nos. 20210108119 and 2021004036, including but not limited to the fluoroolefins identified in Tables 1-3 of U.S. Patent Publication Nos. 20210108119 and 2021004036, the disclosures of each of which are hereby incorporated by reference in their entirety.

[0061] In certain embodiments disclosed herein, the fluoroolefin comprises at least one of HFO-1234yf and HFO-1234ze and may be blended with at least one hydrofluorocarbon. Examples of suitable hydrofluorocarbons include at least one member selected from the following substances: HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa and HFC-227ea. The amount of the hydrofluorocarbon may be in the range of about 25 mol % to about 75 mol %, about 30 mol % to about 60 mol %, and in some cases about 30 mol % to about 50 mol %. In a specific embodiment, the aforementioned amount of hydrofluorocarbon is blended with HFO-1234yf and HFO-1234ze.

[0062] In other embodiments, the refrigerant composition contains at least about 99 weight percent HFO-1234yf and greater than 0 weight percent but less than 1 weight percent of at least one member comprising or selected from the group consisting of HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HFC-245cb, HFO-1225zc, and combinations thereof.

[0063] In other embodiments, the refrigerant composition contains at least about 99.5 weight percent HFO-1234yf and greater than 0 weight percent but less than 0.5 weight percent of at least one member comprising or selected from the group consisting of HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HFC-245cb, and combinations thereof.

[0064] In other embodiments, the refrigerant composition contains at least about 98 weight percent HFO-1234yf and greater than 0 weight percent but less than 2 weight percent of at least one member comprising or selected from the group consisting of HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3-trifluoro-1-propyne, HCFO-1233xf, HFC-245cb, HFO-1225zc, and combinations thereof.

[0065] In other embodiments, the refrigerant composition comprises at least about 99 weight percent HFO-1234ze and greater than 0 weight percent but less than 1 weight percent of at least one member comprising or selected from the group consisting of HFO-1234yf, HFC-245fa, HFC-236fa, HFO-1234ye, and combinations thereof.

[0066] If desired, the blend composition may further include at least one additional member selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113. The amount of the additional member may range from greater than 0 wt % to about 5 wt %, from about 0 wt % to about 2 wt %, and in some cases from about 0 wt % to about 0.5 wt %.

[0067] In a particular embodiment, the foregoing amounts of additional members are blended with at least one of HFO-1234yf and HFO-1234ze.

[0068] In another specific embodiment, the foregoing amounts of additional members are blended with at least one of HFO-1234yf and HFO-1234ze and at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, and HFC-227ea, and in some cases in combination with carbon dioxide, wherein either of HFO-1234yf and HFO-1234ze is present at least 99 weight percent or at least about 99.5 weight percent.

[0069] In order to avoid the oligomerization, homopolymerization or polymerization of fluoroolefins such as HFO-1234yf to form unwanted by-products, inhibitors such as terpenes, terpenoids, terpinenes, linear unsaturated hydrocarbons, such as those disclosed in commonly owned U.S. Patent Publication Nos. 20210108119 and 2021004036, the disclosures of each of which are hereby incorporated by reference in their entirety, are added.

[0070] To avoid oligomerization, homopolymerization or polymerization of fluoroolefins such as HFO-1234yf to form oligomer / polymer byproducts, inhibitors such as terpenes, terpenoids, terpinenes, linear unsaturated hydrocarbons, such as those disclosed in co-owned U.S. Patent Publication Nos. 20210108119 and 2021004036, the disclosures of each of which are hereby incorporated by reference in their entirety, or xylene and methyl styrene inhibitors such as those disclosed in co-owned U.S. Provisional Patent Application No. 63 / 321118, entitled “HYDROCARBONADDITIVES FOR 1234YF AND HFC COMPOSITIONS, METHODS FOR THEIR PRODUCTION, STORAGE AND USAGE” and U.S. Provisional Patent Application No. 63 / 321118, entitled “HYDROCARBONADDITIVES FOR 1234YF AND HFC COMPOSITIONS, METHODS FOR THEIR PRODUCTION, STORAGE AND USAGE” are included. AND USAGE", each of which was filed on March 18, 2022 and is hereby incorporated by reference in its entirety.

[0071] By "inhibitor" is meant at least one compound according to the present invention which reduces (if not eliminates) the conversion of hydrofluoroolefins to oligomers or polymers. Although oligomerization, homopolymerization or polymerization reactions can be accelerated by relatively high temperatures, such reactions can also occur under ambient conditions depending on the concentration and type of initiator (e.g., contaminant). The inhibitor can be used as a free radical inhibitor without affecting the refrigeration system.

[0072] However, while these compositions or blends containing 1234yf inhibitors effectively react with oxygen and / or act as chain transfer agents to terminate polymer chain growth, the presence of the inhibitor may also reduce the purity of the refrigerant or refrigerant blend entering the refrigerant system, depending on the level of inhibitor present. Therefore, in certain embodiments, when the HFO-1234yf or HFO-1234yf blend composition is introduced into the refrigerant system, the stored HFO-1234yf or HFO-1234yf stabilized blend composition is passed through an adsorbent bed such as silica gel to remove the inhibitor and / or stabilizer, thereby ensuring that a high purity HFO-1234yf or HFO-1234yf blend composition enters the refrigerant equipment or system. An additional benefit is that silica gel can also effectively remove water and reduce potential corrosion in the system.

[0073] In addition, the refrigerant equipment may be provided with an oxygen removal subsystem and sensors to determine the presence of air or oxygen, the oxygen removal subsystem comprising one or more oxygen removal devices, such as tubes or towers filled with or containing materials suitable for removing or eliminating oxygen or oxidizing compounds by, for example, deoxygenation or other mechanisms. The tubes / towers may be arranged in parallel or in series and include valved bypass lines associated with or positioned in line with the refrigeration circuit, and the sensors to determine the presence of air or oxygen. The tubes / towers may be arranged in parallel or in series and include valved bypass lines associated with or positioned in line with the refrigeration circuit, and the sensors may be responsive to air / oxygen sensors alone or in combination with a dehumidifying silica bed or desiccant media and an optional UV-dye cartridge.

[0074] The oxygen removal tube / tower usually contains a low-valent transition metal such as Cu that operates at ambient temperature, and effectively reduces the oxygen level of the fluoroolefin composition to less than 5ppm, less than 4ppm, less than 3ppm, less than 2ppm, etc., but does not affect the fluoroolefin molecules, for example, does not crack the C-F bond to facilitate making the Cu-F bond more stable. When there is a single or multiple tower, the oxygen removal tower includes a valve suitable for providing a regeneration medium to the tower after use. When there are multiple oxygen removal towers, include appropriate bypass lines so that the system can remain online and at least one tower is in operation while another tower is regenerated. Other metal-containing reducing agents can also be used for this purpose, and include Ti, V, Mn, Fe, Co, Zn, Ni and Pd, and ascorbate. Other deoxidizers can be used, such as NaHSO 3 、Na 2 SO 3 、Na 2 S 2 O 5 、Na 2 S 2 O 3 、Na 2 S 2 O 4 ; Polyhydroxybenzenes such as pyrogallol; Cr(II) salts; P(=O)H 2 OM, M = alkali metals and alkaline earth metals.

[0075] In addition, the refrigerant equipment described herein may include a system for removing oligomers / byproducts from HFO-1234yf or HFO-1234yf blend compositions (with or without lubricating oil), and include an oil return line so that the lubricant can be returned to the compressor. As used herein, oil return may refer to the ability of a heat transfer composition to carry lubricant through a heat transfer system and return it to the compressor. In other words, in use, it is not uncommon for a portion of the compressor lubricant to be transported from the compressor to other parts of the system by the heat transfer composition. In such systems, if the lubricant is not effectively returned to the compressor, the compressor will eventually fail due to lack of lubricity.

[0076] In some embodiments, the lubricant is a mineral oil lubricant. In some embodiments, the mineral oil lubricant is selected from the group consisting of alkanes (including straight carbon chain saturated hydrocarbons, branched carbon chain saturated hydrocarbons, and mixtures thereof), cycloalkanes (including saturated cyclic and ring structures), aromatic hydrocarbons (those aromatic hydrocarbons having unsaturated hydrocarbons containing one or more rings, wherein one or more rings are characterized by alternating carbon-carbon double bonds) and non-hydrocarbons (those molecules containing atoms such as sulfur, nitrogen, oxygen, and mixtures thereof), and mixtures and combinations thereof.

[0077] Some embodiments may contain one or more synthetic lubricants. In some embodiments, the synthetic lubricant is selected from alkyl substituted aromatic hydrocarbons (such as benzene or naphthalene substituted with linear alkyl groups, branched alkyl groups, or mixtures of linear and branched alkyl groups, generally referred to as alkylbenzenes), synthetic paraffins and cycloalkanes, poly (alpha olefins), polyglycols (including polyalkylene glycols), dibasic acid esters, polyesters, neopentyl esters, polyvinyl ethers (PVE), silicones, silicates, fluorinated compounds, phosphate esters, polycarbonates, and mixtures thereof, meaning mixtures of any lubricant disclosed in this paragraph.

[0078] The lubricant disclosed herein may be a commercially available lubricant. For example, the lubricant may be a paraffinic mineral oil sold by BVA Oils as BVM 100N; 1GS, 3GS and Cycloparaffinic mineral oil sold by 5GS; marketed by Pennzoil under the trademark 372LT, a naphthenic mineral oil sold by Calumet Lubricants under the trademark RO-30 is a naphthenic mineral oil sold by Shrieve Chemicals under the trademark 75. 150 and 500; and branched alkylbenzenes sold by Nippon Oil as HAB 22; and by Castrol in the United Kingdom under the trademark 100 sold as polyol esters (POE); polyalkylene glycols (PAGs) such as RL-488A available from Dow (Dow Chemical, Midland, Michigan, USA), and mixtures thereof, meaning mixtures of any lubricant disclosed in this paragraph.

[0079] The lubricants used with the present invention can be designed for use with hydrofluoroolefins and / or hydrofluorocarbon refrigerants and can be miscible with the compositions disclosed herein under compression refrigeration and air conditioning equipment operating conditions. In some embodiments, the lubricant is selected by considering the given compressor requirements and the environment to which the lubricant will be exposed.

[0080] As used herein, a refrigerant container can be any closed device that holds a supply source of HFO-1234yf or HFO-1234yf blend composition (with or without inhibitor) under pressure, including, but not limited to, for example, a container, a cartridge, a tank, a cylinder, a receptacle that is subsequently used in a refrigeration circuit of a refrigeration device, an air conditioning device, or a heat pump device, optionally including an oxygen or air sensor (not shown). The refrigerant container can also be a refrigeration circuit of a refrigeration device, an air conditioning device, or a heat pump device in which the refrigerant or blend is used. In addition, the refrigerant container can be a storage container or cartridge for fresh refrigerant or a storage container or cartridge for collecting HFO-1234yf or HFO-1234yf blend composition to be recovered.

[0081] As used herein, a refrigeration circuit can be part of any heat transfer system that is fixed in place during operation. A fixed heat transfer system can be located within, attached to, or otherwise associated with any building, or can be a freestanding device located outside a door, such as a soft drink vending machine. These fixed applications may include, but are not limited to, fixed air conditioning units and heat pumps, chillers; high temperature heat pumps; and residential, commercial, or industrial air conditioning systems (including residential heat pumps). In fixed refrigeration applications, the disclosed stabilized or purified compositions or blends can be used in various equipment items, including commercial, industrial, or residential refrigerators and freezers; ice machines; stand-alone coolers and freezers; flooded evaporator coolers; direct expansion coolers; walk-in and reach-in coolers and freezers; and combined systems. In some embodiments, the disclosed compositions can be used in supermarket refrigeration systems. In addition, fixed applications can utilize secondary loop systems in which a secondary fluid is cooled by a primary refrigerant, and the secondary fluid is then pumped to a remote location to provide a cooling effect at the remote location.

[0082] As used herein, a refrigeration circuit may also be part of a mobile heat transfer system and refers to any refrigeration, air conditioning or heating equipment incorporated into a road, rail, sea or air transport unit and includes a refrigeration circuit. In addition, mobile refrigeration or air conditioning units include those devices that are independent of any mobile carrier and are referred to as "combined" systems. Such combined systems include "containers" (sea / land combined transport) and "foldable cargo boxes" (road / rail combined transport). This mobile refrigeration

[0083] A heat transfer medium (also referred to herein as a heat transfer fluid, heat transfer composition, or heat transfer fluid composition or refrigerant composition) is a working fluid used to carry heat from a heat source to a heat sink.

[0084] As used herein, the term "lubricant" means any material added to a composition or compressor (and in contact with any heat transfer composition used within any heat transfer system) that provides lubricity to the compressor to help prevent parts from seizing.

[0085] As used herein, a compatibilizer is a compound that improves the solubility of the hydrofluorocarbon of the disclosed composition in a heat transfer system lubricant. In some embodiments, the compatibilizer improves the oil return of the compressor. In some embodiments, the composition is used with a system lubricant to reduce the viscosity of the oil-rich phase.

[0086] One method embodiment of the present invention involves operating a refrigerant system apparatus by:

[0087] a) providing a pressurized fluoroolefin refrigerant composition comprising at least one of HFO-1234yf and HFO-1234ze, optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, E / ZR-1132, R-1132a and HFC-227ea, and optionally carbon dioxide;

[0088] b) discharging the composition and passing it through a device containing a supported or unsupported oligomerization inhibitor selected from the group consisting of limonene, α-terpinene and α-tocopherol and mixtures of two or more thereof;

[0089] c) adding up to 0.5 wt. % of said agent to a refrigerant composition to form a fluoroolefin stabilized feed that is stable to at least one of oligomerization and polymerization; and

[0090] d) charging the stabilized fluoroolefin feed of c) into a refrigerant plant.

[0091] Another method embodiment of the present invention is directed to operating a refrigerant system apparatus by:

[0092] a) providing pressurized HFO-1234yf;

[0093] b) discharging HFO-1234yf and passing it through a device containing a supply of a supported or unsupported oligomerization inhibitor selected from the group consisting of dextrorotatory limonene, levorotatory limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene and mixtures of two or more thereof;

[0094] c) adding up to 0.5 wt. % of the agent to a refrigerant composition to form an HFO-1234yf feed that is stable to at least one of oligomerization and polymerization; and

[0095] d) charging the stabilized feed of c) into a refrigerant plant.

[0096] Another method embodiment of the present invention is directed to operating a refrigerant system apparatus by:

[0097] a) providing pressurized HFO-1234yf;

[0098] b) discharging HFO-1234yf and passing it through a column containing a supply of at least one oligomerization inhibitor selected from the group consisting of ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutylene, 2-methylbutane, ortho-(o-)xylene, meta-(m-)xylene or para-(p-)xylene and one of the following:

[0099] i. α-Methylstyrene (C 6 H 5 C(CH 3 )=CH 2 ),

[0100] ii.α,2-dimethylstyrene (o-(o)-α,2-dimethylstyrene),

[0101] iii.α,3-dimethylstyrene (m-α,3-dimethylstyrene);

[0102] iv.α,4-dimethylstyrene (p,α-dimethylstyrene);

[0103] c) adding up to 0.5 wt. % of the agent to the refrigerant composition to form a stabilized HFO-1234yf feed that is stable to at least one of oligomerization and polymerization; and

[0104] d) charging the stabilized feed of c) into a refrigerant plant.

[0105] Another method embodiment of the present invention is directed to maintaining the integrity of a refrigerant in a system having at least a refrigeration circuit by:

[0106] Providing at least one of: (1) a stabilized source of HFO-1234yf and HFO-1234ze refrigerant compositions, or (2) an unstabilized source of HFO-1234yf and HFO-1234ze refrigerant compositions;

[0107] Purifying by removing a stabilizer from the HFO-1234yf and HFO-1234ze refrigerant composition (1), or stabilizing by adding an effective amount of an oligomerization inhibitor to the unstabilized HFO-1234yf and HFO-1234ze refrigerant composition (2);

[0108] charging (1) into a refrigeration circuit after the stabilizer of the HFO-1234yf and HFO-1234ze refrigerant composition has been removed, or charging (2) into a refrigeration circuit after an effective amount of an oligomerization inhibitor has been added to an unstabilized source of the HFO-1234yf and HFO-1234ze refrigerant composition;

[0109] · circulate the refrigerant in the circuit; and optionally

[0110] • Remove one of moisture, oxygen and oligomer products and by-products from the installed refrigeration circuit.

[0111] Another method embodiment of the present invention is directed to maintaining the integrity of a refrigerant in a system having at least a refrigeration circuit by:

[0112] · Remove moisture from fluoroolefin stabilized refrigerants in the circuit;

[0113] Fluoroolefin stabilized refrigerants in the drying circuit;

[0114] Optionally detecting the presence of at least one of air, oxygen and moisture;

[0115] · removal of oxygen and oxygen-containing compounds which can initiate oligomerization and / or polymerization of fluoroolefins in the fluoroolefin stabilization feed in the loop; and

[0116] • Removal of one of oligo-polymer products and by-products in the fluoroolefin stabilization feed in the loop.

[0117] In certain embodiments, the refrigeration equipment includes a refrigeration circuit for conveying a composition containing fluoroolefins, the refrigeration circuit comprising at least one compressor, at least one evaporator, at least one condenser, at least one expansion device (which may be an orifice, a capillary tube or an expansion valve) and optionally one or more devices (e.g., pipes, towers, shells for removing oxygen and / or moisture), optionally at least one of the following items: at least one service valve for charging or discharging the composition containing fluoroolefins into the refrigeration equipment; a stabilized refrigerant charging subsystem and / or kit; a purified refrigerant charging subsystem; a subsystem for separating oligomers / polymers; an oligomer / polymer filter and an HFO-1234yf derived oligomer / polymer filter.

[0118] The present invention discloses a stabilized refrigerant charging subsystem, which is provided with accessories suitable for connecting and charging the stabilized refrigerant into a refrigerant circuit or a refrigeration device, including but not limited to:

[0119] 1) a tank filled with HFO-1234yf and a barrel supply of d-limonene,

[0120] 2) a tank filled with HFO-1234yf and a barrel supply of levorotatory limonene,

[0121] 3) a tank filled with HFO-1234yf and a barrel supply of β-pinene,

[0122] 4) a tank filled with HFO-1234yf and a barrel supply of α-pinene,

[0123] 5) a tank filled with HFO-1234yf and a barrel supply of alpha-terpinene,

[0124] 6) a tank filled with HFO-1234yf and a cylinder supply of β-terpinene,

[0125] 7) a tank filled with HFO-1234yf and a cylinder supply of gamma-terpinene,

[0126] 8) a tank filled with HFO-1234yf and a cartridge supply of delta-terpinene,

[0127] 9) a tank filled with HFO-1234yf and a cylinder supply of ethane,

[0128] 10) a tank filled with HFO-1234yf and a cylinder supply of propane,

[0129] 11) a tank filled with HFO-1234yf and a barrel supply of cyclopropane,

[0130] 12) a tank filled with HFO-1234yf and a cylinder supply of propylene,

[0131] 13) a tank filled with HFO-1234yf and a cylinder supply of butane,

[0132] 14) a tank filled with HFO-1234yf and a barrel supply of butene,

[0133] 15) Tanks filled with HFO-1234yf and a barrel supply of isobutane

[0134] 16) a tank filled with HFO-1234yf and a barrel supply of isobutylene,

[0135] 17) a tank filled with HFO-1234yf and a cylinder supply of 2-methylbutane,

[0136] 18) a tank filled with HFO-1234yf and a barrel supply of meta-xylene,

[0137] 19) a tank filled with HFO-1234yf and a barrel supply of o-xylene, or

[0138] 20) A tank filled with HFO-1234yf and a cartridge supply of para-xylene, wherein the tank optionally includes a sensor for detecting air and or oxygen.

[0139] The present invention discloses a stabilized refrigerant charging subsystem, which is provided with accessories suitable for connecting and charging the stabilized refrigerant into a refrigerant circuit or a refrigeration device, including but not limited to:

[0140] 1) a tank filled with HFO-1234ze and a barrel supply of d-limonene, or

[0141] 2) a tank filled with HFO-1234ze and a barrel supply of L-limonene, or

[0142] 3) a tank filled with HFO-1234ze and a barrel supply of β-pinene, or

[0143] 4) a tank filled with HFO-1234ze and a barrel supply of alpha-pinene, or

[0144] 5) a tank filled with HFO-1234ze and a cartridge supply of alpha-terpinene, or

[0145] 6) a tank filled with HFO-1234ze and a cartridge supply of beta-terpinene, or

[0146] 7) a tank filled with HFO-1234ze and a cartridge supply of gamma-terpinene, or

[0147] 8) a tank filled with HFO-1234ze and a cartridge supply of delta-terpinene, or

[0148] 9 A tank filled with HFO-1234ze and a cylinder supply of ethane, or

[0149] 10) a tank filled with HFO-1234ze and a cylinder supply of propane, or

[0150] 11) a tank filled with HFO-1234ze and a barrel supply of cyclopropane, or

[0151] 12) a tank filled with HFO-1234ze and a barrel supply of propylene, or

[0152] 13) a canister filled with HFO-1234ze and a cartridge supply of butane, or

[0153] 14) a tank filled with HFO-1234ze and a barrel supply of butene, or

[0154] 15) a tank filled with HFO-1234ze and a barrel supply of isobutane, or

[0155] 16) a tank filled with HFO-1234ze and a barrel supply of isobutylene, or

[0156] 17) a tank filled with HFO-1234ze and a barrel supply of 2-methylbutane, or

[0157] 18) a tank filled with HFO-1234ze and a barrel supply of meta-xylene, or

[0158] 19) a tank filled with HFO-1234ze and a barrel supply of o-xylene, or

[0159] 20) a tank filled with HFO-1234ze and a barrel supply of para-xylene,

[0160] Any of tanks 1 - 20 optionally includes a sensor for detecting air and / or oxygen.

[0161] The present invention discloses a stabilized refrigerant charging subsystem, which is provided with accessories suitable for connecting and charging the stabilized refrigerant into a refrigerant circuit or a refrigeration device, including but not limited to:

[0162] 1) a canister filled with HFO-1234yf and HFO-1234ze and a barrel supply of d-limonene, or

[0163] 2) a canister filled with HFO-1234yf and HFO-1234ze and a barrel supply of levorotatory limonene, or

[0164] 3) a tank filled with HFO-1234yf and HFO-1234ze and a barrel supply of β-pinene, or

[0165] 4) a tank filled with HFO-1234yf and HFO-1234ze and a barrel supply of alpha-pinene, or

[0166] 5) a canister filled with HFO-1234yf and HFO-1234ze and a cartridge supply of alpha-terpinene, or

[0167] 6) a tank filled with HFO-1234yf and HFO-1234ze and a cartridge supply of beta-terpinene, or

[0168] 7) a tank filled with HFO-1234yf and HFO-1234ze and a cartridge supply of gamma-terpinene, or

[0169] 8) a tank filled with HFO-1234yf and HFO-1234ze and a cartridge supply of delta-terpinene, or

[0170] 9) Tanks filled with HFO-1234yf and HFO-1234ze and a barrel supply of ethane, or

[0171] 10) Tanks filled with HFO-1234yf and HFO-1234ze and a cylinder supply of propane, or

[0172] 11) a tank filled with HFO-1234yf and HFO-1234ze and a barrel supply of cyclopropane, or

[0173] 12) a tank filled with HFO-1234yf and HFO-1234ze and a barrel supply of propylene, or

[0174] 13) a canister filled with HFO-1234yf and HFO-1234ze and a cartridge supply of butane, or

[0175] 14) a tank filled with HFO-1234yf and HFO-1234ze and a barrel supply of butene, or

[0176] 15) a tank filled with HFO-1234yf and HFO-1234ze and a barrel supply of isobutylene, or

[0177] 16) a tank filled with HFO-1234yf and HFO-1234ze and a cylinder supply of 2-methylbutane, or

[0178] 17) a tank filled with HFO-1234yf and HFO-1234ze and a barrel supply of meta-xylene, or

[0179] 18) a tank filled with HFO-1234yf and HFO-1234ze and a barrel supply of o-xylene, or

[0180] 19) Tanks filled with HFO-1234yf and HFO-1234ze and a barrel supply of para-xylene.

[0181] The present invention discloses a stabilized refrigerant charging subsystem, which is provided with accessories suitable for connecting and charging the stabilized refrigerant into a refrigerant circuit or a refrigeration device, including but not limited to:

[0182] 1) a canister filled with HFO-1234yf and HFC-32 and a barrel supply of d-limonene, or

[0183] 2) a canister filled with HFO-1234yf and HFC-32 and a barrel supply of levorotatory limonene, or

[0184] 3) a tank filled with HFO-1234yf and HFC-32 and a barrel supply of β-pinene, or

[0185] 4) a tank filled with HFO-1234yf and HFC-32 and a barrel supply of alpha-pinene, or

[0186] 5) a tank filled with HFO-1234yf and HFC-32 and a barrel supply of alpha-terpinene, or

[0187] 6) a tank filled with HFO-1234yf and HFC-32 and a cartridge supply of beta-terpinene, or

[0188] 7) a tank filled with HFO-1234yf and HFC-32 and a cartridge supply of gamma-terpinene, or

[0189] 8) a tank filled with HFO-1234yf and HFC-32 and a cartridge supply of delta-terpinene, or

[0190] 9) Tanks filled with HFO-1234yf and HFC-32 and a barrel supply of ethane, or

[0191] 10) Tanks filled with HFO-1234yf and HFC-32 and a cylinder supply of propane, or

[0192] 11) Tanks filled with HFO-1234yf and HFC-32 and a barrel supply of cyclopropane, or

[0193] 12) a tank filled with HFO-1234yf and HFC-32 and a barrel supply of propylene, or

[0194] 13) canisters filled with HFO-1234yf and HFC-32 and a cartridge supply of butane, or

[0195] 14) Tanks filled with HFO-1234yf and HFC-32 and a barrel supply of butene, or

[0196] 15) a canister filled with HFO-1234yf and HFC-32 and a barrel supply of isobutylene, or

[0197] 16) a tank filled with HFO-1234yf and HFC-32 and a barrel supply of 2-methylbutane, or

[0198] 17) a tank filled with HFO-1234yf and HFC-32 and a barrel supply of meta-xylene, or

[0199] 18) a tank filled with HFO-1234yf and HFC-32 and a barrel supply of o-xylene, or

[0200] 19) a tank filled with HFO-1234yf and HFC-32 and a barrel supply of para-xylene,

[0201] The tank optionally includes a sensor for detecting air and or oxygen.

[0202] The present invention discloses a stabilized refrigerant charging subsystem, which is provided with accessories suitable for connecting and charging the stabilized refrigerant into a refrigerant circuit or a refrigeration device, including but not limited to:

[0203] 1) a canister filled with HFO-1234yf and HFC-125 and a barrel supply of d-limonene, or

[0204] 2) a canister filled with HFO-1234yf and HFC-125 and a barrel supply of levorotatory limonene, or

[0205] 3) a tank filled with HFO-1234yf and HFC-125 and a barrel supply of β-pinene, or

[0206] 4) a canister filled with HFO-1234yf and HFC-125 and a barrel supply of alpha-pinene, or

[0207] 5) a canister filled with HFO-1234yf and HFC-125 and a cartridge supply of alpha-terpinene, or

[0208] 6) a tank filled with HFO-1234yf and HFC-125 and a cartridge supply of beta-terpinene, or

[0209] 7) a tank filled with HFO-1234yf and HFC-125 and a cartridge supply of gamma-terpinene, or

[0210] 8) a tank filled with HFO-1234yf and HFC-125 and a cartridge supply of delta-terpinene, or

[0211] 9) Tanks filled with HFO-1234yf and HFC-125 and a barrel supply of ethane, or

[0212] 10) Tanks filled with HFO-1234yf and HFC-125 and a cylinder supply of propane, or

[0213] 11) Tanks filled with HFO-1234yf and HFC-125 and a barrel supply of cyclopropane, or

[0214] 12) a tank filled with HFO-1234yf and HFC-125 and a barrel supply of propylene, or

[0215] 13) Canisters filled with HFO-1234yf and HFC-125 and a cartridge supply of butane, or

[0216] 14) a canister filled with HFO-1234yf and HFC-125 and a barrel supply of butene, or

[0217] 15) a tank filled with HFO-1234yf and HFC-125 and a barrel supply of isobutylene, or

[0218] 16) a tank filled with HFO-1234yf and HFC-125 and a barrel supply of 2-methylbutane, or

[0219] 17) a tank filled with HFO-1234yf and HFC-125 and a barrel supply of meta-xylene, or

[0220] 18) a tank filled with HFO-1234yf and HFC-125 and a barrel supply of o-xylene, or

[0221] 19) a tank filled with HFO-1234yf and HFC-125 and a barrel supply of para-xylene,

[0222] Any of tanks 1 - 19 optionally includes a sensor for detecting air and / or oxygen.

[0223] The present invention discloses a stabilized refrigerant charging subsystem, which is provided with accessories suitable for connecting and charging the stabilized refrigerant into a refrigerant circuit or a refrigeration device, including but not limited to:

[0224] 1) a canister filled with HFO-1234yf, HFC-32, and HFC-125 and a barrel supply of d-limonene, or

[0225] 2) a canister filled with HFO-1234yf, HFC-32, and HFC-125 and a barrel supply of levorotatory limonene, or

[0226] 3) tanks filled with HFO-1234yf, HFC-32 and HFC-125 and a barrel supply of beta-pinene, or

[0227] 4) canisters filled with HFO-1234yf, HFC-32 and HFC-125 and a barrel supply of alpha-pinene, or

[0228] 5) a canister filled with HFO-1234yf, HFC-32 and HFC-125 and a cartridge supply of alpha-terpinene, or

[0229] 6) a canister filled with HFO-1234yf, HFC-32 and HFC-125 and a cartridge supply of beta-terpinene, or

[0230] 7) a canister filled with HFO-1234yf, HFC-32 and HFC-125 and a cartridge supply of gamma-terpinene, or

[0231] 8) a canister filled with HFO-1234yf, HFC-32 and HFC-125 and a cartridge supply of delta-terpinene, or

[0232] 9) Tanks filled with HFO-1234yf, HFC-32 and HFC-125 and a barrel supply of ethane, or

[0233] 10) Tanks filled with HFO-1234yf, HFC-32, and HFC-125 and a cylinder supply of propane, or

[0234] 11) Tanks filled with HFO-1234yf, HFC-32 and HFC-125 and a barrel supply of cyclopropane, or

[0235] 12) Tanks filled with HFO-1234yf, HFC-32, and HFC-125 and a barrel supply of propylene, or

[0236] 13) Canisters filled with HFO-1234yf, HFC-32, and HFC-125 and a cartridge supply of butane, or

[0237] 14) Tanks filled with HFO-1234yf, HFC-32 and HFC-125 and a barrel supply of butene, or

[0238] 15) Tanks filled with HFO-1234yf, HFC-32, and HFC-125 and a barrel supply of isobutylene, or

[0239] 16) tanks filled with HFO-1234yf, HFC-32 and HFC-125 and a barrel supply of 2-methylbutane, or

[0240] 17) Tanks filled with HFO-1234yf, HFC-32, and HFC-125 and a barrel supply of meta-xylene, or

[0241] 18) Tanks filled with HFO-1234yf, HFC-32 and HFC-125 and a barrel supply of o-xylene, or

[0242] 19) tanks filled with HFO-1234yf, HFC-32 and HFC-125 and a barrel supply of para-xylene,

[0243] Any of tanks 1 - 19 optionally includes a sensor for detecting air and / or oxygen.

[0244] The present invention discloses a stabilized refrigerant charging subsystem, which is provided with accessories suitable for connecting and charging the stabilized refrigerant into a refrigerant circuit or a refrigeration device, including but not limited to:

[0245] 1) a canister filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of d-limonene, or

[0246] 2) a canister filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of levorotatory limonene, or

[0247] 3) a canister filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of beta-pinene, or

[0248] 4) a canister filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of alpha-pinene, or

[0249] 5) a canister filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of alpha-terpinene, or

[0250] 6) a tank filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of beta-terpinene, or

[0251] 7) a tank filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of gamma-terpinene, or

[0252] 8) a tank filled with HFO-1234yf and HFC-134 / HFC-134a and a cartridge supply of delta-terpinene, or

[0253] 9) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of ethane, or

[0254] 10) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a and a cylinder supply of propane, or

[0255] 11) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of cyclopropane, or

[0256] 12) a tank filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of propylene, or

[0257] 13) Canisters filled with HFO-1234yf and HFC-134 / HFC-134a and a cartridge supply of butane, or

[0258] 14) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of butene, or

[0259] 15) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of isobutylene, or

[0260] 16) a tank filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of 2-methylbutane, or

[0261] 17) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of meta-xylene, or

[0262] 18) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of o-xylene, or

[0263] 19) Tanks filled with HFO-1234yf and HFC-134 / HFC-134a and a barrel supply of para-xylene.

[0264] The present invention discloses a stabilized refrigerant charging subsystem, which is provided with accessories suitable for connecting and charging the stabilized refrigerant into a refrigerant circuit or a refrigeration device, including but not limited to:

[0265] 1) a canister filled with HFO-1234yf, HFC-32, HFC-125, and HFC-134 / HFC-134a and a barrel supply of d-limonene, or

[0266] 2) a canister filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of levorotatory limonene, or

[0267] 3) canisters filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of beta-pinene, or

[0268] 4) canisters filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of alpha-pinene, or

[0269] 5) canisters filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of alpha-terpinene, or

[0270] 6) tanks filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of beta-terpinene, or

[0271] 7) tanks filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of gamma-terpinene, or

[0272] 8) tanks filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a cartridge supply of delta-terpinene, or

[0273] 9) Tanks filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of ethane, or

[0274] 10) Tanks filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a cylinder supply of propane, or

[0275] 11) Tanks filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of cyclopropane, or

[0276] 12) Tanks filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of propylene, or

[0277] 13) Canisters filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a cartridge supply of butane, or

[0278] 14) Tanks filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of butene, or

[0279] 15) Tanks filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of isobutylene, or

[0280] 16) Tanks filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of 2-methylbutane, or

[0281] 17) Tanks filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of meta-xylene, or

[0282] 18) a tank filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of ortho-xylene, or a tank filled with HFO-1234yf, HFC-32, HFC-125 and HFC-134 / HFC-134a and a barrel supply of para-xylene,

[0283] Any of tanks 1 - 18 optionally includes a sensor for detecting air and / or oxygen.

[0284] The present invention discloses a stabilized refrigerant charging subsystem, which is provided with accessories suitable for connecting and charging the stabilized refrigerant into a refrigerant circuit or a refrigeration device, including but not limited to:

[0285] 1) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a and a barrel supply of d-limonene, or

[0286] 2) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a, and a barrel supply of levo-limonene, or

[0287] 3) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, HFO-1132a and a barrel supply of β-pinene, or

[0288] 4) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132, HFO-1132a and a barrel supply of alpha-pinene, or

[0289] 5) a canister filled with HFO-1234yf and HFO-1234ze and a cartridge supply of alpha-terpinene, or

[0290] 6) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a, and a cartridge supply of beta-terpinene, or

[0291] 7) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a, and a cartridge supply of gamma-terpinene, or

[0292] 8) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a, and a cartridge supply of delta-terpinene, or

[0293] 9) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a and a barrel supply of ethane, or

[0294] 10) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a and a cylinder supply of propane, or

[0295] 11) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a and a barrel supply of cyclopropane, or

[0296] 12) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a, and a barrel supply of propylene, or

[0297] 13) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a and a cartridge supply of butane, or

[0298] 14) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a and a cartridge supply of butene, or

[0299] 15) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a and a barrel supply of isobutylene, or

[0300] 16) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a and a cartridge supply of 2-methylbutane, or

[0301] 17) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a and a barrel supply of meta-xylene, or

[0302] 18) a tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a and a barrel supply of ortho-xylene, or

[0303] 19) A tank filled with HFO-1234yf and optionally at least one additional refrigerant selected from HFO-1234ze, HFC-32, HFC-125, HFC-134a, HFC-152a, E / Z-HFO-1132 and HFO-1132a and a barrel supply of para-xylene.

[0304] In one embodiment, the refrigeration circuit includes a first service valve and a second service valve and a stabilized refrigerant charging subsystem, which includes a pressurized source of a self-contained fluoroolefin refrigerant composition, a circulating cartridge and an oligomerization / polymerization inhibitor for stabilizing the fluoroolefin refrigerant composition, and the cartridge has an outlet connected to the high-pressure side of the service valve and in fluid communication for charging the stabilized fluoroolefin refrigerant into the circuit, and the circuit is a closed circuit.

[0305] In one embodiment, the refrigerant line of the refrigeration equipment or the refrigerant line of the refrigerant circuit includes or is modified to include at least one of a), b), c) and d) in series or in parallel:

[0306] a) circulation treatment zones containing materials for drying the refrigerant composition or blend and / or containing deoxygenation reagents suitable for removing oxygen from the fluoroolefin-containing mixture, optionally at room temperature (e.g., 20° C. to 30° C.). Each treatment zone or combination of treatment zones can be regenerated. Reagents that can be used to remove oxygen include, but are not limited to, Ti, V,

[0307] Mn, Fe, Co, Zn, Ni and Pd and ascorbate;

[0308] b) a tube or capsule or cartridge of an oligomer inhibitor stabilizer, wherein the stabilizer is supported on a pellet or other inert medium, or is unsupported, such as a self-supporting solid or liquid added to a refrigerant composition or blend through a fluoroolefin stream. Various oligomer or polymer inhibitor stabilizers include, but are not limited to, inhibitors described in U.S. Patent Publication Nos. US20210108119 and US202100430368 and d-limonene, levo-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene and mixtures of two or more thereof;

[0309] c) means for dehumidification, and

[0310] d) A separation filter system to remove oligomer / polymer products and / or by-products that may be formed during the circulation of the refrigerant composition or blend.

[0311] In other embodiments, the refrigerant line of the mobile refrigeration equipment or the refrigerant line of the mobile refrigerant circuit includes or is modified to include at least one of a), b), c) and d) in series or in parallel:

[0312] a) circulation treatment zones containing materials for drying the refrigerant composition or blend and / or containing deoxygenation reagents suitable for removing oxygen from the fluoroolefin-containing mixture, optionally at room temperature (e.g., 20° C. to 30° C.). Each treatment zone or combination of treatment zones can be regenerated. Reagents that can be used to remove oxygen include, but are not limited to, Ti, V,

[0313] Mn, Fe, Co, Zn, Ni and Pd and ascorbate;

[0314] b) a tube or capsule or cartridge of an oligomer inhibitor stabilizer, wherein the stabilizer is supported on a pellet or other inert medium, or is unsupported, such as a self-supporting solid or liquid added to a refrigerant composition or blend through a fluoroolefin stream. Various oligomer or polymer inhibitor stabilizers include, but are not limited to, inhibitors described in U.S. Patent Publication Nos. US20210108119 and US202100430368 and d-limonene, levo-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene and mixtures of two or more thereof;

[0315] c) means for dehumidification, and

[0316] d) A separation filter system to remove oligomer / polymer products and / or by-products that may be formed during the circulation of the refrigerant composition or blend.

[0317] In other embodiments disclosed herein, a mobile refrigeration system in a transport vehicle can be taken to a service center having a recovery, recycling and recharging machine (RRRM) and connected to one or more of the following systems: these systems are used to (1) add stabilizer to the source of HFO-1234yf or HFO-1234yf blend to be loaded, (2) remove stabilizer from the stabilized HFO-1234yf or stabilized HFO-1234yf blend to be loaded, (3) attach a stabilizer injection kit for a system running on OpteonTM products or R448Af to the system or dose stabilizer into the system.

[0318] One embodiment of the present invention includes refrigeration systems having: a self-contained pressurized source of fluoroolefins comprising at least 2,3,3,3-tetrafluoropropene; a refrigerant circuit capable of circulating the refrigerant and comprising at least a first inline loading valve; a first flow line providing a fluid-controlled flow between the pressurized processing units; a second flow line providing a fluid-controlled flow between the processing units and the first inline loading valve on the downstream side of the compressor; at least one or more inline flow-through oxygen removal tubes / towers containing deoxygenation reagent units suitable for removing oxygen and oxidizing compounds, including but not limited to zero-valent or low-valent transition metals and reduced oxides of transition metals, selected from Cu, Ti, V, Mn, Fe, Co, Zn, Ni and Pd, from a mixture containing fluoroolefins at room temperature (e.g., 20°C to 30°C). The zero-valent or low-valent transition metals and reduced oxides of transition metals are commercially available or can be prepared by heating transition metal oxides at elevated temperatures (100° C. to 300° C.) in a reservoir such as a tube or tower in the presence of a reducing agent such as hydrogen. Examples of metal oxides suitable for reduction in this manner include CuO, TiO 2 、V 2 O 5 , Mn 2 O 3 , Fe 2 O 3 、Co 3 O 4 , ZnO, NiO and PdO. Other deoxygenation agents include ascorbate, NaHSO 4 、Na 2 SO 3 、Na 2 S 2 O 5 、Na 2 S 2 O 3 、Na 2 S 2 O 2 , solutions of polyhydroxybenzene compounds such as pyrogallol; Ti(III) salts, Cr(II) salts, Sn(II) salts, Fe(II) salts; nitrites and hypophosphites. Oxygen can be removed from the fluoroolefin composition by passing the fluoroolefin mixture through a tube / tower or bed of a deoxygenating agent at a temperature of about 20°C to about 30°C.

[0319] While some metals / metal oxides are known oxygen scavengers, based on the technical literature, these compounds are generally very reactive toward fluoroolefins. Surprisingly, certain reduced metal oxides of Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd perform the intended oxygen scavenging function but do not cleave the C-F bonds in 2,3,3,3-tetrafluoropropene or other fluoroolefins. The metals / metal oxides present in known oxygen scavengers have been used to cleave the C-F bonds to form more stable metal fluoride bonds, which remove oxygen without the intended C-F bond cleavage. C-F bond cleavage in fluoroolefins (C=CF) is very common. Metal-fluorine bonds (e.g., Cu-F ~ 431 kJ / mol) are more stable than metal-oxygen bonds (e.g., Cu-O ~ 343 kJ / mol), so there is an energetic driving force for the reaction of the metal oxide (product of oxygen scavenging) with the organofluorine compound. Therefore, they can be used to scavenge inert gases (Ar, N 2 It was not expected and not obvious that materials that remove oxygen from 2,3,3,3-tetrafluoropropene could remove oxygen contaminants from 2,3,3,3-tetrafluoropropene.

[0320] In other embodiments, stored fresh HFO-1234yf or HFO-1234yf blend compositions containing stabilizers are passed through a filter capable of removing stabilizers from the HFO-1234yf or HFO-1234yf blend compositions, and to provide high purity HFO-1234yf or HFO-1234yf blend compositions for loading into the refrigerant equipment and systems described herein, these recycled compositions may be passed through an adsorbent filter bed such as silica gel capable of removing inhibitors, their oxidized derivatives, and water to reduce potential corrosion in the system.

[0321] Another embodiment of the present invention comprises: a refrigerant charge kit comprising a stabilized fluoroolefin-containing composition in a sealed cartridge, the composition comprising HFO-1234yf and HFO-1234ze, optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa and HFC-227ea, and optionally carbon dioxide; and a refrigerant charge kit comprising a sealed refrigerant cartridge containing the stabilized fluoroolefin composition, the composition comprising at least HFO-1234yf as a refrigerant component and up to 0.5 weight percent of an oligomer inhibitor comprising at least one of dextrorotatory limonene, levorotatory limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene; and a tube for connecting the discharge end of the refrigerant cartridge to a valve of a refrigerant circuit. In certain embodiments, the stabilized refrigerant blend may contain any of the above-mentioned lubricants.Thus, a refrigerant pack may contain any of the disclosed refrigerant blends that have been stabilized but do not contain a lubricant.

[0322] The injector kit embodiment of the present invention is provided with accessories suitable for connecting the lubricant containing stabilizer to the refrigeration equipment, including but not limited to:

[0323] a. A cartridge filled with POE lubricant and up to 0.5 wt% d-limonene.

[0324] b. a cylinder filled with POE lubricant and up to 0.5 wt. % levorotatory limonene,

[0325] c. a cylinder filled with POE lubricant and up to 0.5 wt.% β-pinene,

[0326] d. a cylinder filled with POE lubricant and up to 0.5 wt.% α-pinene,

[0327] e. a cylinder filled with POE lubricant and up to 0.5 wt.% α-terpinene,

[0328] f. a cylinder filled with POE lubricant and up to 0.5 wt. % β-terpinene,

[0329] g. a cylinder filled with POE lubricant and up to 0.5 wt. % γ-terpinene,

[0330] h. a cylinder filled with POE lubricant and up to 0.5 wt. % delta-terpinene,

[0331] i. a cylinder filled with POE lubricant and up to 0.5 wt% ethane,

[0332] j. A cartridge filled with POE lubricant and up to 0.5 wt. % propane,

[0333] k. a cylinder filled with POE lubricant and up to 0.5 wt. % cyclopropane,

[0334] l. A cylinder filled with POE lubricant and up to 0.5 wt% propylene,

[0335] m. a cylinder filled with POE lubricant and up to 0.5 wt. % butane,

[0336] n. a cylinder filled with POE lubricant and up to 0.5 wt. % butene,

[0337] o. A cylinder filled with POE lubricant and up to 0.5 wt. % isobutylene,

[0338] p. a cylinder filled with a POE lubricant and up to 0.5 wt. % isobutylene,

[0339] q. a cartridge filled with POE lubricant and up to 0.5 wt. % methylbutane,

[0340] r. A cylinder filled with POE lubricant and up to 0.5 wt. % m-xylene,

[0341] s. A cylinder filled with POE lubricant and up to 0.5 wt. % o-xylene,

[0342] t. a cylinder filled with POE lubricant and up to 0.5 wt. % para-xylene,

[0343] u. A cylinder filled with a mineral oil lubricant and up to 0.5% by weight of dextrorotatory limonene,

[0344] v. a cylinder filled with a mineral oil lubricant and up to 0.5% by weight of levorotatory limonene,

[0345] w. a cylinder filled with a mineral oil lubricant and up to 0.5 wt. % β-pinene,

[0346] x. a cylinder filled with a mineral oil lubricant and up to 0.5 wt. % α-pinene,

[0347] y. a cartridge filled with a mineral oil lubricant and up to 0.5 wt. % α-terpinene,

[0348] z. a cylinder filled with a mineral oil lubricant and up to 0.5 wt. % β-terpinene,

[0349] aa. A cylinder filled with a mineral oil lubricant and up to 0.5 wt. % γ-terpinene,

[0350] bb. a cartridge filled with a mineral oil lubricant and up to 0.5 wt. % delta-terpinene,

[0351] cc. a cylinder filled with a mineral oil lubricant and up to 0.5 wt. % ethane,

[0352] dd. A cartridge filled with a mineral oil lubricant and a maximum of 0.5 wt. % propane,

[0353] ee. a cartridge filled with a mineral oil lubricant and up to 0.5 wt. % cyclopropane,

[0354] ff. A cylinder filled with a mineral oil lubricant and up to 0.5 wt. % propylene,

[0355] gg. a cartridge filled with a mineral oil lubricant and up to 0.5% by weight of butane,

[0356] hh. A cylinder filled with a mineral oil lubricant and up to 0.5 wt. % butene,

[0357] ii. a cartridge filled with a mineral oil lubricant and up to 0.5 wt. % isobutane,

[0358] jj. A cylinder filled with a mineral oil lubricant and up to 0.5 wt. % isobutylene,

[0359] kk. A cartridge filled with a mineral oil lubricant and up to 0.5 wt. % 2-methylbutane,

[0360] ll. A cylinder filled with a mineral oil lubricant and up to 0.5% by weight of m-xylene,

[0361] mm. A cylinder filled with a mineral oil lubricant and up to 0.5 wt. % o-xylene,

[0362] nn. A cylinder filled with a mineral oil lubricant and up to 0.5 wt. % p-xylene,

[0363] oo. A cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of dextrorotatory limonene,

[0364] pp. A cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of levorotatory limonene,

[0365] qq. a cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % of β-pinene,

[0366] rr. a cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % α-pinene,

[0367] ss. a cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of alpha-terpinene,

[0368] ss. a cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % beta-terpinene,

[0369] uu. A cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of gamma-terpinene,

[0370] vv. A cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of delta-terpinene,

[0371] ww. a cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of ethane,

[0372] xx. a cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % propane,

[0373] yy. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % cyclopropane,

[0374] zz. A cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of propylene,

[0375] aaa. A cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of butane,

[0376] bbb. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % butene,

[0377] ccc. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % isobutylene,

[0378] ddd. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % isobutane,

[0379] eee. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % 2-methylbutane,

[0380] fff filled with alkylbenzene lubricant and up to 0.5% by weight of m-xylene cylinder,

[0381] ggg. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % o-xylene,

[0382] hhh. Cylinders filled with alkylbenzene lubricant and up to 0.5 wt. % para-xylene.

[0383] The injector kit embodiment of the present invention is provided with accessories suitable for connecting the refrigerant composition containing the stabilizer, including but not limited to:

[0384] a. a cylinder filled with POE lubricant and up to 0.5 wt. % dextrorotatory limonene,

[0385] b. a cylinder filled with POE lubricant and up to 0.5 wt. % levorotatory limonene,

[0386] c. a cylinder filled with POE lubricant and up to 0.5 wt.% β-pinene,

[0387] d. a cylinder filled with POE lubricant and up to 0.5 wt.% α-pinene,

[0388] e. a cylinder filled with POE lubricant and up to 0.5 wt.% α-terpinene,

[0389] f. a cylinder filled with POE lubricant and up to 0.5 wt. % β-terpinene,

[0390] g. a cylinder filled with POE lubricant and up to 0.5 wt. % γ-terpinene,

[0391] h. a cylinder filled with POE lubricant and up to 0.5 wt. % delta-terpinene,

[0392] i. a cylinder filled with POE lubricant and up to 0.5 wt% ethane,

[0393] j. A cartridge filled with POE lubricant and up to 0.5 wt. % propane,

[0394] k. a cylinder filled with POE lubricant and up to 0.5 wt. % cyclopropane,

[0395] l. A cylinder filled with POE lubricant and up to 0.5 wt% propylene,

[0396] m. a cylinder filled with POE lubricant and up to 0.5 wt. % butane,

[0397] n. a cylinder filled with POE lubricant and up to 0.5 wt. % butene,

[0398] o. A cylinder filled with POE lubricant and up to 0.5 wt. % isobutylene,

[0399] p. a cylinder filled with POE lubricant and up to 0.5 wt. % methylbutane,

[0400] q. a cylinder filled with POE lubricant and up to 0.5 wt. % meta-xylene,

[0401] r. A cylinder filled with POE lubricant and up to 0.5 wt. % o-xylene,

[0402] s. A cylinder filled with POE lubricant and up to 0.5 wt. % p-xylene,

[0403] t. a cylinder filled with a mineral oil lubricant and up to 0.5% by weight of dextrorotatory limonene,

[0404] u. A cylinder filled with a mineral oil lubricant and up to 0.5% by weight of levorotatory limonene,

[0405] v. a cylinder filled with a mineral oil lubricant and up to 0.5 wt. % β-pinene,

[0406] w. a cylinder filled with a mineral oil lubricant and up to 0.5 wt. % α-pinene,

[0407] x. a cartridge filled with a mineral oil lubricant and up to 0.5 wt. % alpha-terpinene,

[0408] y. a cartridge filled with a mineral oil lubricant and up to 0.5 wt. % beta-terpinene,

[0409] z. a cylinder filled with a mineral oil lubricant and up to 0.5 wt. % γ-terpinene,

[0410] aa. A cartridge filled with a mineral oil lubricant and up to 0.5 wt. % delta-terpinene,

[0411] bb. a cartridge filled with a mineral oil lubricant and up to 0.5 wt. % ethane,

[0412] cc. a cartridge filled with a mineral oil lubricant and up to 0.5 wt. % propane,

[0413] dd. A cartridge filled with a mineral oil lubricant and up to 0.5 wt. % cyclopropane,

[0414] ee. A cartridge filled with a mineral oil lubricant and up to 0.5 wt. % propylene,

[0415] ff. A cartridge filled with a mineral oil lubricant and up to 0.5% by weight of butane,

[0416] gg. a cylinder filled with a mineral oil lubricant and up to 0.5% by weight of butene,

[0417] hh. A cylinder filled with a mineral oil lubricant and up to 0.5 wt. % isobutylene,

[0418] ii. a cartridge filled with a mineral oil lubricant and up to 0.5 wt. % 2-methylbutane,

[0419] jj. A cylinder filled with a mineral oil lubricant and up to 0.5 wt. % m-xylene,

[0420] kk. A cylinder filled with a mineral oil lubricant and up to 0.5 wt. % o-xylene,

[0421] ll. A cylinder filled with a mineral oil lubricant and up to 0.5% by weight of p-xylene,

[0422] mm. a cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % dextrorotatory limonene,

[0423] nn. A cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of levorotatory limonene,

[0424] oo. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % β-pinene,

[0425] pp. A cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of α-pinene,

[0426] qq. a cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % alpha-terpinene,

[0427] rr. a cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % beta-terpinene,

[0428] ss. a cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of gamma-terpinene,

[0429] tt. a cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % delta-terpinene,

[0430] uu. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % ethane,

[0431] vv. A cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of propane,

[0432] ww. a cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of cyclopropane,

[0433] xx. a cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % propylene,

[0434] yy. A cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of butane,

[0435] zz. A cylinder filled with an alkylbenzene lubricant and up to 0.5% by weight of butene,

[0436] aaa. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % isobutane,

[0437] bbb. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % isobutylene,

[0438] ccc. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % 2-methylbutane,

[0439] ddd. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % meta-xylene,

[0440] eee. A cylinder filled with an alkylbenzene lubricant and up to 0.5 wt. % o-xylene, or

[0441] fff. Cylinders filled with alkylbenzene lubricant and up to 0.5 wt. % p-xylene.

[0442] Embodiments of the invention will now be described with reference to the accompanying non-limiting drawings. Figure 1A first system embodiment 100 for adding a stabilizer to HFO-1234yf or an HFO-1234yf blend as described herein is shown. A valved cartridge 105 contains HFO-1234yf or an HFO-1234yf blend and is in fluid communication with an inlet side of a stabilizer cartridge 110. When valve 115 is opened, pressurized HFO-1234yf or an HFO-1234yf blend flows through cartridge 110 and picks up an inhibitor to provide an HFO-1234yf composition containing up to 0.5 wt % inhibitor, between 0.001 wt % and 0.1 wt % inhibitor, between 0.001 wt % and 0.2 wt % inhibitor; between 0.001 wt % and 0.3 wt % inhibitor, between 0.001 wt % and 0.4 wt % inhibitor, between 0.001 wt % and 0.01 wt % inhibitor; and between 0.001 wt % and 0.01 wt % inhibitor. % to 0.02 wt % inhibitor; 0.001 wt % to 0.03 wt % inhibitor; 0.001 wt % to 0.04 wt % inhibitor; 0.001 wt % to 0.05 wt % inhibitor; 0.01 wt %, 0.02 wt %, 0.03 wt %, 0.04 wt %, 0.05 wt %, 0.06 wt %, 0.07 wt %, 0.08 wt %, 0.09 wt % to 0.1 wt % inhibitor; and 0.01 wt % to 0.05 wt % inhibitor and all values ​​and ranges therebetween.

[0443] When a change in the phase of the refrigerant is involved, the refrigeration circuit 101 typically includes a high-side service valve 115, a filter / dryer 120, a device 125 such as an expansion valve, an evaporator 130, a low-side service valve 135, a compressor 140, and a condenser 145 in sequence. However, if the refrigerant circuit does not rely on changing the phase of the refrigerant to transfer energy, fewer components will be involved. The order of components 115, 120, 125, 135, 140, 145 can be arranged as shown, but additional components may be included if necessary. Once stabilized, the 1234yf refrigerant leaves the cartridge 110 and is metered / charged into the refrigeration circuit 101 through the high-side service valve 115. The stabilized refrigerant then flows through the filter / dryer 120, a device such as an expansion valve 125, the evaporator 130, the low-side service valve 135, and the compressor 140 in sequence, and the compressed stabilized refrigerant then passes through the heat exchanger / condenser 145, then through the valve 115 and recirculates. Alternatively, the liquid refrigerant may also be throttled by a low-side service valve 135 disposed upstream of the compressor. The cartridge 110 includes at least one of the various oligomer or polymer inhibitor stabilizers discussed above, including but not limited to dextrorotatory limonene, levorotatory limonene, beta-pinene, alpha-pinene, alpha-terpinene, beta-terpinene, gamma-terpinene, and delta-terpinene, and including mixtures of two or more thereof. The refrigeration circuit 101 may be a new, existing, or retrofitted system requiring fresh refrigerant, additional refrigerant, replacement refrigerant, or a start-up supply of refrigerant, etc.

[0444] Although a single 'stabilizer' cartridge 110 or filter / dryer 120 is shown, multiple cartridges 110 containing the same or different inhibitors and / or multiple filters / dryers 120 containing different filter media arranged in series or in parallel may be used. The two stabilizer cartridges may be arranged in series / sequentially with a bypass line (not shown) so that the refrigerant flowing from the tank 105 may flow through the first cartridge 110 but bypass the second stabilizer cartridge. Alternatively, the refrigerant from the tank 105 may flow through the first cartridge 110 and then bypass the second cartridge.

[0445] Figure 2A second system embodiment 200 is shown for removing stabilizers from stabilized HFO-1234yf or stabilized HFO-1234yf blend composition refrigerants before charging the purified refrigerant into the refrigeration circuit to provide high-purity HFO-1234yf or HFO-1234yf blend compositions. The present invention describes a refrigerant cylinder / drum that charges liquid refrigerant into a high-side service valve 215. Alternatively, the liquid refrigerant may also be throttled by a low-side service valve (not shown) arranged upstream of the compressor. In this case, the valve cylinder 205 will contain stabilized HFO-1234yf, with or without HFO-1234ze, optionally with additional refrigerant components, and will be arranged to be in fluid communication with the inlet side of a stabilizer removal tower / filter 250 as described herein (e.g., a silica bed that can remove inhibitors as described herein). The refrigeration circuit 201 includes, in sequence, a service valve 215, a filter 220, an expansion device 255 such as an expansion valve, an evaporator 230, a compressor 240, and a heat exchanger / condenser 245. When a cartridge valve (not shown) is opened, liquid HFO-1234yf or a HFO-1234yf blend refrigerant containing, for example, HFO-1234ze flows to and through the filter 250 and removes the stabilizer. Although a single filter is shown, multiple filters in series or parallel may also be used, including a bypass line (not shown).

[0446] Figure 3 shows the use of a system for removing O 2 Embodiment 300 of using a stand-alone filter and / or a polymer / filter in a compressor suction line. 2 Valved bypass lines are shown around both the filter and polymer filter to allow for actual removal and replacement in the system, as well as to depict the concept that they may only be needed in certain circumstances. Additionally, the refrigeration circuit 301 may be provided with a refrigerant cylinder (not shown) for charging liquid into a high-side service valve (not shown) downstream of the heat exchanger / condenser 345. Alternatively, liquid HFO-1234yf or a blend of HFO-1234yf containing, for example, HFO-1234ze may also be throttled and a low-side service valve (not shown) may be utilized. Alternative alternatives include the filter / dryer 320 and the O 2 Filter 316 is integrated into a package (not shown), polymer filter 317 is moved upstream of the expansion device (e.g., valve 365), or all three filters 320, 316, and 317 are integrated into a package and located upstream of the expansion device 365. As shown, in Figure 3 In the embodiment, the refrigeration circuit 301 includes a filter / dryer 320 and an O 2filter 316 (wherein valve 360 ​​and optional controller (not shown) are used to control fluid flow), an expansion device such as valve 365, an evaporator 330, a polymer filter 317 (wherein valve 361 and optional controller (not shown) are used to control fluid flow), a compressor 340 and a heat exchanger / condenser 345.

[0447] Figure 4 An embodiment 400 is shown that includes an integrated oil separator / polymer filter 470 for returning oil to the oil in a return line 471 of the compressor 440. The refrigeration circuit 401 includes, in sequence, a filter / dryer 420, a device 465 such as an expansion valve, an evaporator 430, a compressor 440, an integrated oil separator / polymer filter 470 and a return line 471, and a heat exchanger / condenser 445.

[0448] Figure 5 Similar to Figure 4 , but shows an embodiment 500 using an integrated oil / polymer filter 575 for allowing compressor oil to flow from the compressor sump to the compressor lubricating surfaces via a shaft driven oil pump or an external oil pump. The refrigeration circuit 501 includes, in sequence, a filter / dryer 520, an expansion device such as a valve 565, an evaporator 530, a compressor 540, an integrated oil separator / polymer filter 575 and a return line 571, and a heat exchanger / condenser 545.

[0449] Figure 6 An embodiment 600 of an integrated system is shown that includes a refrigeration circuit 601 with a stabilizer injection kit 680 for systems running on Opteon™ products or R448A without stabilizer, or otherwise dosing more stabilizer into a system already loaded with refrigerant. The injection stabilizer will be charged to the system via the low side service valve 635 or any other suitable location.

[0450] The refrigeration circuit 601 includes, in sequence, a filter / dryer 620, a device such as an expansion valve 665, an evaporator 630, a low-side service valve 635, a stabilizer injection kit 680, a compressor 640, a heat exchanger 645, and a service valve 615. The kit 680 includes one of a stabilized lubricant, a stabilized HFO-1234yf or a HFO-1234yf blend containing, for example, HFO-1234ze, a refrigerant, and a stabilized refrigerant / lubricant mixture, wherein the stabilizer is selected from the group consisting of dextrorotatory limonene, levorotatory limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene, and δ-terpinene, and mixtures of two or more thereof, or ethane, propane, cyclopent ... Propane, propylene, a cylinder filled with an alkylbenzene lubricant and up to 0.5 wt % isobutylene, 2-methylbutane, meta-xylene, ortho-xylene or para-xylene, one of the following: α,-methylstyrene; α,2-dimethylstyrene; α,3-dimethylstyrene; or α,4-dimethylstyrene, in an amount effective to reduce or eliminate oligomerization / polymerization of the HFO-1234yf component of the refrigerant, for example, 0.02 wt % to 0.3 wt %.

[0451] In certain embodiments disclosed herein, at least a) a service valve suitable for charging a fluoroolefin refrigerant composition into the refrigerant circuit; b) a stabilized refrigerant charging subsystem; a purified refrigerant charging subsystem, which optionally includes an air / oxygen detector; d) a subsystem for removing oxygen and / or oxidizing compounds, which includes a deoxidizer and is optionally responsive to an air / oxygen detector; e) a subsystem for separating oligomers / polymers; and f) an oligomer / polymer filter can be added to an existing system as a separate component or as an integrated system.

[0452] Example 1 to Example 4

[0453] Towards The tube (0.5 inch OD, 15 inch long, 0.34 inch wall thickness) was filled with 8cc Al 2 O 3 CuO (40 wt%) was loaded. The reaction mixture was heated to 175 °C in a Lindbreg furnace with 50 sccm H 2 / N2(50% H 2 ) The catalyst was reduced for 8 hours. After the reactor was cooled to room temperature, CF containing air of different concentrations was introduced at 10 sccm-20 sccm (standard cubic centimeters per minute). 3 CF=CH 2 (HFO-1234yf). During the operation, the air concentration was measured by GC, indicating that O 2 The concentration is less than 5ppm.

[0454] Example Air concentration (ppm) <![CDATA[Processed O 2 Concentration (ppm)]]> 1 1,000 <5 2 2,000 <5 3 3,000 <5 4 6,000 <5

[0455] Example 5 to Example 10

[0456] 30 g of HFO-1234yf containing various concentrations of d-limonene was passed through 20 g of silica gel (200 mesh) or 50 mL of mineral oil. GC showed that the residual inhibitor content was less than 5 ppm.

[0457]

[0458] Although certain aspects, embodiments and principles have been described above, it should be understood that this description is exemplary only and not limiting of the present invention or the appended claims. The aforementioned various aspects, embodiments and principles can be used alone or in combination with each other.

Claims

1. A refrigerant system comprising a refrigeration circuit for conveying a fluoroolefin refrigerant composition, the refrigerant circuit comprising at least one compressor, at least one expansion device, at least one evaporator, at least one condenser, at least one dryer for dehumidification and optionally at least one component selected from the group consisting of: a) at least one service valve configured to charge the refrigerant circuit with a fluoroolefin refrigerant composition; b) Stabilized refrigerant loading subsystem; c) a purified refrigerant charge subsystem, which optionally includes an air / oxygen detector; d) a subsystem for removing oxygen and / or oxidative compounds, comprising a deoxidizer and optionally responsive to said air / oxygen detector; e) a subsystem for oligomer / polymer separation; and f) Oligo / polymer filters.

2. The refrigerant system according to claim 1, wherein the refrigeration circuit is a closed circuit and contains the fluoroolefin refrigerant composition, the fluoroolefin refrigerant composition comprising: at least one of HFO-1234yf and HFO-1234ze, Optionally, at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa, E / ZR-1132 and HFC-227ea, and optionally carbon dioxide.

3. The refrigerant system of claim 1, wherein the at least one drier for dehumidification is a single filter drier.

4. The refrigerant system of claim 1, wherein the at least one dryer is a single dryer containing an adsorbent bed for dehumidification.

5. The refrigerant system of claim 1, wherein the at least one dryer is a single tower housing a filter section and a dryer section.

6. The refrigerant system of claim 1 , wherein the refrigeration circuit comprises a first service valve and a second service valve and a stabilized refrigerant charging subsystem, the stabilized refrigerant charging subsystem comprising a pressurized source of a self-contained fluoroolefin refrigerant composition, a flow-through cartridge, and an oligomerization / polymerization inhibitor for stabilizing the fluoroolefin refrigerant composition, and wherein the flow-through cartridge has an outlet connected to and in fluid communication with a high side of the service valve for charging the circuit with stabilized fluoroolefin refrigerant.

7. The refrigeration system of claim 1 wherein the refrigeration circuit comprises a first service valve, a purified refrigerant charge subsystem, the purified refrigerant charge subsystem comprising a self-contained pressurized source of a stabilizer-containing fluoroolefin refrigerant composition in fluid communication with a separation column to remove the stabilizer and provide a purified stabilizer-free fluoroolefin refrigerant composition, the column having an outlet connected to and in fluid communication with a high side of the first service valve.

8. The refrigerant system of claim 1 wherein there is a single compressor having a discharge outlet connected to and in fluid communication with the polymer separator.

9. The refrigerant system of claim 7 further comprising a second service valve and a subsystem for charging the stabilized fluoroolefin refrigerant composition to the low side of the second service valve.

10. The refrigerant system of claim 1, wherein a plurality of dehumidifying dryers are arranged serially in fluid communication with the circuit.

11. The refrigerant system of claim 1 wherein a plurality of dehumidifying dryers are arranged in line with and in fluid communication with the circuit, and wherein the circuit optionally includes a valved bypass for a second dehumidifying dryer.

12. A method for operating a refrigerant device, the method comprising: a) providing a fluoroolefin refrigerant composition and optionally a lubricant, the fluoroolefin refrigerant composition comprising: at least one of HFO-1234yf and HFO-1234ze, Optionally, at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa, E / ZR-1132, R-1132a, and HFC-227ea, and optionally carbon dioxide; b) discharging the fluoroolefin refrigerant composition and passing it through a column containing a supported oligomerization / polymerization inhibitor comprising at least one member selected from the group consisting of limonene, α-terpinene and α-tocopherol and a mixture of two or more thereof; c) adding up to 0.5 wt. % of said oligomerization / polymerization inhibitor to said fluoroolefin refrigerant composition to form a fluoroolefin stabilized feed that is stable to oligomerization and / or polymerization; as well as d) charging said stabilized fluoroolefin feed of c) into said refrigerant equipment.

13. The method of claim 12, wherein the refrigerant equipment comprises a refrigerant circuit and step d) comprises charging the fluoroolefin stabilized feed of c) directly into the refrigerant circuit.

14. The method of claim 12, wherein the tower is a cartridge.

15. The method of claim 13, wherein the cartridge contains an inert material that supports the oligomerization / polymerization inhibitor.

16. The method of claim 13, wherein the oligomerization / polymerization inhibitor is in liquid form and the cartridge is configured to pass the fluoroolefin refrigerant composition under the driving force of the fluoroolefin refrigerant composition to add up to 0.5 wt. % of the oligomerization / polymerization inhibitor to the fluoroolefin refrigerant composition.

17. The method of claim 16 further comprising circulating the stabilized fluoroolefin charge in the refrigerant equipment.

18. The method according to any one of claims 16 or 17, wherein the refrigeration equipment comprises a refrigeration circuit through which the fluoroolefin stabilized feed is continuously circulated, the method further comprising at least one of the following steps: a) removing moisture from the fluoroolefin stabilized feed in said loop; b) drying said fluoroolefin stabilized feed in said loop; c) optionally in response to an air / oxygen detector associated with a vapor space or fluoroolefin stabilized feed in said refrigeration loop, removing oxygen and oxidizing compounds capable of initiating oligomerization and / or polymerization of fluoroolefins in said fluoroolefin stabilized feed in said loop; and d) removing one of oligomerization-polymerization products and by-products from the fluoroolefin stabilized feed in the loop.

19. The process of claim 18, comprising removing moisture from the fluoroolefin stabilized feed in the loop.

20. The method of claim 12, wherein the oligomerization / polymerization inhibitor comprises a member selected from the group consisting of limonene, alpha-terpinene, and alpha-tocopherol, and a mixture of two or more thereof.

21. The method of claim 12, wherein the fluoroolefin refrigerant composition comprises: i. a fluoroolefin comprising at least HFO-1234yf, and ii. Optional HFC, said HFC comprising at least one of HFC-32, HFC-125 and HFC-134a.

22. A method of maintaining the integrity of a refrigerant in a system having at least a refrigeration circuit, the method comprising: Providing at least one of: (1) a stabilized source of HFO-1234yf and HFO-1234ze refrigerant compositions, or (2) an unstabilized source of HFO-1234yf and HFO-1234ze refrigerant compositions; Purifying by removing any stabilizer from the HFO-1234yf and HFO-1234ze refrigerant composition (1), or stabilizing by adding an effective amount of an oligomerization inhibitor to the unstabilized HFO-1234yf and HFO-1234ze refrigerant composition (2), and subsequently loading (1) or (2) into the refrigeration circuit; · Circulating refrigerant in the installed refrigeration circuit, and optionally • Remove one of moisture, oxygen and oligomer products and by-products from the installed refrigeration circuit.

23. A method of maintaining the integrity of a refrigerant in a system having at least a refrigeration circuit, the method comprising: · continuously circulating a refrigerant composition containing a fluoroolefin in the refrigeration circuit; as well as - passing the circulating fluoroolefin-containing refrigerant composition through at least one dehumidification dryer, at least one deoxygenation tower and at least one oligomer or polymer product or by-product filter / separator.

24. The method of claim 23, wherein the fluoroolefin-containing refrigerant composition comprises at least one of HFO-1234yf and HFO-1234ze; optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, 236fa and HFC-227ea; and optionally carbon dioxide.

25. The method of claim 23, wherein the system contains stabilized sources of HFO-1234yf and HFO-1234ze tetrafluoropropenes, and the stabilizer inhibits oligomerization / polymerization of the tetrafluoropropenes.

26. The method of claim 23, wherein passing the circulating fluoroolefin-containing refrigerant composition through the dehumidifying dryer and the deoxygenation tower occurs upstream of a compressor in the refrigerant circuit.

27. The method of claim 26, wherein the discharge from the compressor is passed through the oligomer or polymer product or by-product separator / filter.

28. A refrigeration system, comprising: a) a pressurized source of a fluoroolefin comprising at least 2,3,3,3-tetrafluoropropene; b) a refrigerant circuit configured to circulate a refrigerant and comprising a first inline loading valve; c) a first flow line providing fluid controlled communication between the pressurization source and a flow inhibitor cartridge; d) a second flow line providing fluid controlled communication between the flow-through inhibitor cartridge and a high side of the first inline loading valve; e) optionally at least one or more inline flow-through deoxygenation towers containing a deoxygenating agent capable of removing oxygen without cleaving the C-F bonds of the fluoroolefins; and f) an optional inline inhibitor removal column in said first flow line.

29. The system of claim 28, wherein the pressurized source comprises HFO-1234yf and HFO-1234ze; optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa, and HFC-227ea; and optionally carbon dioxide.

30. A refrigerant loading kit, the refrigerant loading kit comprising: a) a sealed fluoroolefin-containing refrigerant cylinder, wherein the fluoroolefin-containing refrigerant comprises HFO-1234yf and HFO-1234ze; optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa and HFC-227ea; and optionally carbon dioxide; b) a packaged cartridge filled with an oligomer inhibitor; c) a first tube configured to connect a discharge end of the refrigerant cartridge to an inlet end of the packaged cartridge; and d) A second tube configured to connect the outlet end of the packaged cartridge to a valve of a refrigerant circuit.

31. The refrigeration system of claim 28, wherein the inhibitor comprises an effective amount of about 0.02 ppm to about 0.3 ppm of at least one member selected from the group consisting of dextrorotatory limonene, levorotatory limonene, alpha-pinene, beta-pinene, alpha-terpinene, beta-terpinene, gamma-terpinene and delta-terpinene and a mixture of two or more styrenes.

32. The method of claim 12, wherein the inhibitor comprises at least one member selected from the group consisting of dextrorotatory limonene, levorotatory limonene, α-pinene, β-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene and a mixture of two or more styrenes in an amount of about 0.02 ppm to about 0.3 ppm.

33. The refrigeration system of claim 28, wherein the inhibitor comprises an effective amount of about 0.02 ppm to about 0.3 ppm of at least one member selected from the group consisting of ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutylene, 2-methylbutane, m-xylene, o-xylene or p-xylene, one of the following: alpha,-methylstyrene; α,2-dimethylstyrene; α,3-dimethylstyrene; and α,4-dimethylstyrene.

34. The method of claim 12, wherein the inhibitor comprises at least one member selected from the group consisting of ethane, propane, propylene, butane, butene, isobutane, isobutylene, 2-methylbutane, m-xylene, o-xylene or p-xylene, one of the following: α,-methylstyrene; α,2-dimethylstyrene; α,3-dimethylstyrene; and α,4-dimethylstyrene in an amount of about 0.02 ppm to about 0.3 ppm.

35. A refrigerant loading kit, the refrigerant loading kit comprising: A sealed refrigerant cartridge containing a stabilized fluoroolefin composition comprising HFO-1234yf and HFO-1234ze, optionally at least one hydrofluorocarbon selected from the group consisting of HFC-32, HFC-125, HFC-134a, HFC-152a, R-236fa and HFC-227ea, and optionally carbon dioxide.

36. A refrigerant loading kit, the refrigerant loading kit comprising: A sealed refrigerant cylinder containing a stabilized fluoroolefin composition, the composition comprising at least HFO-1234yf as a refrigerant component and up to 0.5 wt. % of an oligomer inhibitor, the oligomer inhibitor comprising at least one of: d-limonene, levo-limonene, β-pinene, α-pinene, α-terpinene, β-terpinene, γ-terpinene and δ-terpinene and a mixture of two or more thereof; and A tube is configured to connect the discharge end of the refrigerant cylinder to a valve of a refrigerant circuit.

37. A refrigerant loading kit, the refrigerant loading kit comprising: A sealed refrigerant cylinder containing a stabilized fluoroolefin composition, the composition comprising at least HFO-1234yf as a refrigerant component and less than 0.5 weight percent of an oligomer inhibitor, the oligomer inhibitor comprising at least one of ethane, propane, cyclopropane, propylene, butane, butene, isobutylene, 2-methylbutane, meta-xylene, ortho-xylene or para-xylene, one of the following: α,-methylstyrene; α,2-dimethylstyrene; α,3-dimethylstyrene; or α,4-dimethylstyrene; and A tube is configured to connect the discharge end of the refrigerant cylinder to a valve of a refrigerant circuit.

38. A refrigerant loading kit, the refrigerant loading kit comprising: A cylinder filled with POE, mineral oil or alkylbenzene lubricant and less than 0.5 weight percent of ethane or propane or cyclopropane or propylene or butane or butylene or isobutane or isobutylene or 2-methylbutane or meta-xylene or ortho-xylene or para-xylene; and a pipe configured to connect the discharge end of the refrigerant cylinder to a valve of a refrigerant circuit.

39. A refrigerant system comprising a refrigeration circuit for conveying a fluoroolefin refrigerant composition, the refrigerant system comprising: a) at least one dryer for dehumidification, and optionally at least one of the following: b) at least one service valve configured to charge said fluoroolefin refrigerant composition into said refrigerant circuit; c) Stabilized refrigerant is charged into the subsystem; d) a purified refrigerant charge subsystem, which is optionally included in an air / oxygen detector; e) a subsystem for removing oxygen and / or oxidative compounds, comprising a deoxidizer and optionally responsive to said air / oxygen detector; f) a subsystem for oligomer / polymer separation; and g) Oligomeric / polymeric filters.

40. An apparatus for addition to or integration with a refrigerant system having a refrigerant circuit, the apparatus comprising at least one of the following: a) at least one service valve adapted to charge the refrigerant circuit with a fluoroolefin refrigerant composition; b) Stabilized refrigerant loading subsystem; c) a purified refrigerant charge subsystem, which is optionally included in an air / oxygen detector; d) a subsystem for removing oxygen and / or oxidative compounds, comprising a deoxidizer and optionally responsive to said air / oxygen detector; e) a subsystem for oligomer / polymer separation; and f) Oligo / polymer filters.

41. A transportation service center, comprising the system according to any one of claims 1, 28 and 39.

42. A transportation service center, comprising the device according to claim 40.

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